Admission is free. It's at 8th and F Streets NW, Washington, D.C. 20001, open 11:30 a.m.-7:00 p.m. daily. From three you can stroll to the nearby Restaurant District around 7th to 8th Sts or Washington's Chinatown restaurants, or you could also tour the International Spy Museum, which is fascinating and fun (especially for kids), also at 8th and F Sts. It usually opens earlier, from 9 AM.
Seconding PUGACHEV’s and Albion Wilde’s recommendation for the National Portrait Gallery. It put faces to names. Painters have idealized portraits since time began, but there were a surprising number that portrayed people in all their fallible humanity, warts and all.
The Hope Diamond is a rock. A shiny rock, but still a rock in the middle of a claustrophobia-inducing crowd of people.
Definitely bug-off spray for the fireworks on the Mall - the one and only time I went I got eaten alive.
There is a nice little bar near the spy museum, I drank a beer while DH & the kids did the Spy Museum. Lots of interesting people there. :)